Complex mixtures of ions and processes for deposition

ABSTRACT

A composition and method for providing a wear-resistant and fuel-saving coating on metals, particularly metal surfaces within internal combustion engines. A source of ammonium ions, an alkali metal in an aqueous medium, and the coating metal to be applied to the surface are combined to produce an electrolyte solution comprising a complex ion mixture. The electrolyte solution can be used to deposit the coating metal on conductive substrates. The coating metal may comprise phosphorus, sulfur, carbon, bismuth, boron, silicon, and combinations thereof. The electrolyte solution can be dehydrated in a hydrocarbon medium, thus providing novel materials for use as lubricating oil additives and as fuel additives. These new surfaces may significantly reduce coefficient of friction, smooth the flame front, reduce corrosion, enhance fuel economy, and reduce hydrocarbon emissions when used in internal combustion engines.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation-in-part of U.S. patentapplication Ser. No. 10/936,333 filed Sep. 8, 2004, and entitled“Complex Mixtures of Ions and Processes for Deposition ofSilicon/Nitrogen Coatings on Surfaces.”

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not Applicable.

BACKGROUND OF THE INVENTION

1. Technical Field of the Invention

The present invention relates to the field of aqueous solutionsincluding mixtures of inorganic and organic ions, their preparation, andapplications. More particularly, the present invention relates tocompositions and methods for the preparation of performance enhancingsurfaces that can comprise a phosphorous, sulfur, carbon, boron, orbismuth surface conversion that can prolong metal parts, including metalparts of internal combustion engines. The new conversion surfacesimprove fuel consumption and decrease hydrocarbon pollutants usingcomplex aqueous mixtures of ions.

2. Description of the Related Art

The successful deposition of silicon has long been sought in the platingart. For example, U.S. Pat. No. 4,029,747 to Merkl, entitled “Method OfPreparing Inorganic And Polymeric Complexes And Products So Produced”describes purportedly new compositions and methods of manufacture formulti-metal amides. Merkl describes these complexes as suitable for “theproduction of soaps and detergents” and “for plating of one or more ofthe various metals of groups I-VIII of periodic table on varioussubstrates.”

A characteristic of the Merkl inorganic polymeric complexes with respectto plating is that through the use of these complexes it is purportedlypossible to plate certain metals which have not been previously capableof plating, for example, to the refractory metals such as titanium,tantalum, and niobium, as well as to silicon. While silicon has beenpreviously reported as being deposited by vacuum deposition andsputtering techniques, there appears to be no record of the successfulplating of silicon metal, according to Merkl.

Merkl describes several experiments wherein silicon is put into solutionwith an ammonium hydroxide, an alkali metal hydroxide, and anon-alkaline metal. Several analytical methods described in the Merklpatent show that nitrogen can be stabilized in an alkaline medium. Merkldescribes a process that requires an endothermic phase and an exothermicphase in order to make the polymeric complexes. Merkl teaches that ifthe reaction is not as described, then silicates will form and cannot bereversed rendering the resulting product useless for polymeric purposes.As will be demonstrated, this is no longer true in accordance with thepresent invention.

Silicon is an abundant, brittle, nonmetallic element that is found insand, clay, bauxite, granite and many other minerals. Silicon chemicalswere first developed in the 1860's and have since found wide uses inmany industrial applications as sodium silicate, potassium silicate,ferrosilicon and high purity silicon. Sodium and potassium silicates areused as desiccants, components of detergents, fire retardants, incements, and as additives in steel manufacturing to harden the steel.See, generally, Silicon Chemistry: From the Atom to Extended Systems”,P. Jutzi and U. Schubert (eds.) (2003) WILEY-VCH Verlag GmbH & Co. KGaA,Weinheim, ISBN 3-527-30647-1.

U.S. Pat. No. 4,634,540 to Ropp, describes several methods of makingsodium and/or potassium silicates by reacting silicon rocks with analkali metal hydroxide. Ammonium ions were not used in the Roppreactions.

Many attempts have been made in the past to improve the surfaceproperties of metals in order to widen their applications. For example,U.S. Pat. No. 4,533,606 to Teng et al. describes methods and aqueouscompositions said to be suitable for electrodepositing co-deposits ofzinc, silicon, and phosphorus on metal substrates. However, onlyco-deposits including phosphorus and zinc with silicon are described,and the electro deposition requires substantial time.

U.S. Pat. Nos. 5,084,263 and 5,310,419 to McCoy et al., describe morerapid electroplating with “inorganic polymeric water complexes” of manymetals, however, silicon is not among them. U.S. Pat. No. 5,540,788 toDefalco et al. describes forming an iron-phosphate conversion surface insitu, in internal combustion engines. However, the methods described byboth McCoy et al. and Defalco at al. require the use of strongly acidiccomponents in their preparation.

Silicon nitrides were developed in the 1960s and 70s in attempts todevelop fully dense, high strength ceramics as replacements for steel,particularly in internal combustion engines. Studies on silicon nitridesshowed high temperature properties for retaining high strength andoxidation resistance. Silicon nitrides come in at least threecategories, namely: 1) reaction bonded silicon nitride; 2) hot pressedsilicon nitride; and 3) sintered silicon nitrides. The sintered siliconnitrides have higher density and are more widely used than the other twoprocesses. The important properties of silicon nitride surfaces include:good density, high-temperature strength, superior thermal shockresistance, excellent wear resistance, good fracture toughness,prevention of mechanical fatigue and creep, good oxidation resistance,and enhanced lubricity.

However, the difficulty of the manufacturing processes has kept thismaterial from becoming a major product in the replacement of metals formany applications. The manufacture of silicon nitride ceramic bodies canbe relatively complex. For example, U.S. Pat. No. 6,784,131 to Komatsuet al. describes a silicon nitride sintered body constituting a wearresistant member that is produced by at least the following steps:mixing a predetermined amount of a sintering assistant agent, a requiredadditive, such as an organic binder, and a compound of Al, Mg, AlN, Tior the like, to a fine powder of silicon nitride, which has apredetermined fine average grain size and contains a very small amountof oxygen; molding into a compact having a predetermined shape viamolding methods such as single-axial pressing method, the die-pressingmethod or the doctor-blade method, rubber-pressing method, CIP (coldisostatic pressing) or the like. Multiple heating steps to remove theadditives and binders, sintering at high temperature under vacuum, andhigh temperature curing, follow the molding steps.

While the method of manufacture has several drawbacks, silicon nitrideshave nevertheless found uses in components of internal combustionengines such as glow plugs for quicker start-up, pre-combustion chambersfor lower emissions, and in turbochargers for reduced lag and emissionscontrol. Wider use of silicon nitrides can only be achieved by bettermanufacturing procedures that will drive down costs and make partscompetitive. Accordingly, the ability to deposit silicon nitridesurfaces on metals using an aqueous solution would be of tremendouscommercial value to the automotive industry, not to mention theaerospace industry and others.

The search for methods of improving fuel economy and reducing toxicemissions has been the driving force behind the development of siliconnitride coatings for small parts for internal combustion engines.Recently, automobile regulations such as regulations regarding fuelconsumption and exhaust emissions have become more and more severe. Thereasons behind this are well known, and include environmental problemssuch as air pollution, acid rain, and the like, and policies for theprotection of finite global hydrocarbon resources out of concerns fordepletion of petroleum energy and minimization of greenhouse gases. As acountermeasure, reducing fuel consumption is, at least arguably, themost cost-effective solution, at present.

Many of the approaches of materials science that have historically beenavailable for increasing efficiency and improving performance are alsobeing constrained, however. For example, as described by U.S. Pat. No.6,784,143 to Locke et al., the need for less toxic emissions fromexhaust gases is becoming more demanding, mainly because ofenvironmental problems such as the emission of pollutants such ashydrocarbons, carbon monoxide and nitrogen oxides. Catalytic convertersin the exhaust systems of automobiles have been used for some time nowto reduce the emission of pollutants. Such converters generally use acombination of catalytic metals, such as platinum or variations thereofand metal oxides, and are installed in the exhaust streams, e.g., theexhaust pipes of automobiles to convert the toxic gases to non-toxicgases. Phosphorus components, such as the decomposition products of thewear-reducing additive zinc dithiophosphate, an effective anti-wear oiladditive, are believed to poison the catalyst in these converters. Also,it is likely that sulfur components poison the catalyst components usedin reduction of nitrogen oxides. Notwithstanding the above, Locke stillrequires significant, though reduced, concentrations of phosphorus andsulfur.

Thus, there is clear automotive industry pressure towards reducing thephosphorus and sulfur content in fuel and lubricating oil additivecompositions for emissions considerations rather than in increasing themfor wear-reduction purposes. Reducing the phosphorus concentrations can,obviously, be readily accomplished by reducing the allowable amount ofzinc dithiophosphate that can be used in the oil composition, but thiscomes at the expense of diminishing the anti-wear and anti-oxidantproperties of the oil (and fuel) composition. As is well known in theart, engine manufacturers have already experienced substantialdifficulties with premature engine failures as a result of changing fueland oil specifications to reduce the concentration of known anti-wearcomponents (notably sulfur).

Accordingly, a process providing for the electroless in situ depositionof silicon and nitrogen on the wearing surfaces of metals, including butnot limited to metals in the internal combustion would be both abreakthrough in engine technology and of substantial commercialimportance.

BRIEF SUMMARY OF SOME OF THE PREFERRED EMBODIMENTS

It is thus an object of the present invention to overcome thedeficiencies of the prior art and thereby to provide unique and new usesfor a chemical composition of silicon, silicon/nitrogen/alkali, orsilicon/nitrogen bimetallic metal.

In some embodiments, there is provided a composition and method forproviding a wear-resistant and fuel-saving coating on metals,particularly metal surfaces within internal combustion engines. In onepreferred embodiment, a source of ammonium ions, an alkali metal in anaqueous medium, and a coating metal to be applied to the surface arecombined to produce an electrolyte solution comprising a complex ionmixture. In other embodiments, the electrolyte solution can be used todeposit the coating metal on conductive substrates. In some preferredembodiments, the coating metal may comprise phosphorus, sulfur, carbon,bismuth, boron, silicon, and combinations thereof. In other preferredembodiments, the electrolyte solution may be dehydrated in a hydrocarbonmedium, thus providing novel materials for use as lubricating oiladditives and as fuel additives. In other preferred embodiments thesenew surfaces may significantly reduce coefficient of friction, smooththe flame front, reduce corrosion, enhance fuel economy, and/or reducehydrocarbon emissions when used in internal combustion engines.

As will be described in detail below, we have found that when sodiumand/or potassium silicate are dissolved in water and ammonium hydroxideis placed in the aqueous solution, and then an alkali metal hydroxide,including without limitation potassium hydroxide and sodium hydroxide,is added into the aqueous solution, which is then heated, that newcomplex mixtures of ions are formed, which we postulate may includesilicon complexes. The temperature may preferably be raised rapidly byheating to above 180° F. The reaction may preferably be allowed to gothrough its own further exotherm, and produce a clear viscous solutionwith a pH of 14 and a Specific Gravity of 1.1. A panel of 1010 steelimmersed in the solution for 30 seconds then formed a visible film onthe metal that was extremely slippery. The immersed panel and anuntreated panel were then immersed in a solution of 3% sodium chloridefor three days, extracted, and allowed to dry. There was visible redcorrosion on the untreated panel and no corrosion on the treated panel,indicating the new surface imparted superior corrosion resistance. Aswill be recognized by those skilled in the art, other silicates may ofcourse be used without departing from the scope of the present inventionincluding, without limitation, metasilicates (inosilicates),cyclosilicates, orthosilicates (nesosilicates), and silicates producedby reacting other silicate minerals, although sodium and potassiumsilicates are currently most preferred.

The Merkl patent discussed above recites at col. 10, 11. 57-64: “On theother hand, if the feed of the alkali hydroxide is too slow, and asresult, there is insufficient NH₂ group formation and hydrogen release,the eroded non-alkaline metal tends to bind with the metal in the formof a salt, such as sodium silicate. When this occurs, it does not appearpossible to reverse the reaction to achieve the product of the desiredcomplexes.” Accordingly, Merkl teaches that an alkali metal silicatecannot be used to form inorganic polymeric complexes. Merkl does notpostulate the ability to form new polymeric complexes using sodium orpotassium silicates.

Example 1 of Merkl describes a low purity silicon/potassium/ammoniareaction. The reaction phase is described with an endothermic phase thatlasted for six hours and then an exothermic reaction that lasted for 45minutes. Using the same elements as described in the Merkl Example, alow purity ferrosilicon of 98.5% silicon and 1.5% iron was reacted withammonium hydroxide and potassium hydroxide and water. The solution washeated to above 180° F. and exhibited an exotherm within 20 minutes. Noendothermic reaction was involved. The solution continued on its ownexotherm for several minutes and then stopped. A viscous, clear solutionwith a specific gravity of 1.2 resulted. After cooling down, a panel of1010 steel was immersed in the solution and a clear, tenacious, thinfilm was formed on the panel. The surface formed was very slippery. Thepanel was then left in the open, humid air of Houston, Tex. for thirtydays and no red corrosion was visible. Accordingly, the requirement ofMerkl for an endothermic reaction appears to be unnecessary with thepresent invention.

We experimented further with the postulated silicon complexes describedherein to determine if the complexes could be used as a lubricating oiladditive and/or as a fuel additive. The complexes, as will be describedin more detail later, were dehydrated in a lubricating oil by heatingthe oil until all the water content had been removed and the oil becameclear and bright. At a certain elevated temperature, the chemical saltspresent in the complex precipitated out of the oil solution. A simpletest was devised to determine if there was any active ingredientremaining in the oil solution. A panel of 1010 steel was immersed forone minute in the oil solution. The panel was extracted from the oilsolution, wiped dry, and a noticeable, thin, bright film was present onthe surface of the panel, which is taken as an indication that theactive ingredient was still available for deposition on a conductivesubstrate from a hydrocarbon solution. There are no prior references ofwhich the inventors are aware claiming to make silicon soluble in ahydrocarbon solution, much less using the complexes for deposition ofsilicon/nitrogen or silicon/nitrogen bimetallic surfaces, to conductivesubstrates in internal combustion engines.

The inventive oil solutions were also tested in small two-cycle enginesto determine if the silicon would aid in improving fuel economy oftwo-cycle engines. Surprisingly, as detailed below, these tests showed apositive trend in improving fuel economy and reducing emissions fromtwo-cycle engines.

One of the preferred embodiments of the present invention comprisessolubilizing silicon/nitrogen and silicon/nitrogen bimetallic complexesin hydrocarbons and alcohols, and using the hydrocarbons to carry theactive silicon/nitrogen to the surface of conductive substrates in thecombustion chamber while the engine is running. This provides a new,easy, and non-obvious method of forming a thin silicon/nitrogen film onmetal surfaces in engines, gearboxes, differentials, etc. by aninexpensive process.

Hydrogen is postulated as having an effect on the activity levelexperienced in these postulated silicon complexes. According to Merkl atcol. 21, 11. 14-19, “In a further study using mass spectroscopy it hasbeen observed that nitrogen and atomic hydrogen are released by theinorganic polymeric complex. The atomic hydrogen appears to be releasedall the way from room temperature through 1550° C. The nitrogen isreleased at 875° C.” As will be detailed later, in accordance with thepresent invention, hydrogen preferably has an effect on the fuel economyof the hydrocarbons.

As discussed above, Ropp describes methods of making sodium and/orpotassium silicates but does not describe use of ammonium ions. Ropp (atcol. 2, 1. 63—col.3, 1. 40) describes extensively the release ofhydrogen gas from the silicate composition as follows: “The formation ofthis complex Si(OH)_(y) allows an exchange of hydrogen atoms andelectrons between the silicon particle surface and the trapped oil tohydrogenate certain oil components to produce gaseous products and tothin the oil. The soluble silicate thereby produced has a definiteeffect on oil viscosity as well as affecting the direction ofmodification of certain oil components . . . . The oil modificationagent is negatively charged silicon particle surfaces in a basic medium. . . . The negatively charged hydroxyl ion transfers its charge to thesemi-conducting silicon surface of the particle and attaches itselfthereto. When two or more hydroxyl ions are attached to the siliconsurface, hydrogen gas is produced . . . .”

The Merkl patent teaches, by using mass spectrometry analytictechniques, that Atomic Hydrogen is released from asilicon/ammonium/alkali metal complex throughout a significanttemperature range from ambient up to 1550° C. Ropp teaches that hydrogenobtained from an alkali silicate solution modifies unrefinedhydrocarbons. We postulate in accordance with the present invention thatthe hydrogen available in our silicate compositions will act as ahydrogenation catalyst on refined fuels in the combustion chamber. Thebreaking up of larger hydrocarbon molecules into smaller gaseousmolecules will have an effect on improving the combustion properties ofrefined fuels such as diesel and gasoline. It is further postulated thatthe hydrogenation of the refined hydrocarbon will give a percussioneffect to the combustion process. It was well established thattetraethyl lead imparted a percussion effect to the combustion processand resulted in better burn characteristics and better fuel economy.

We have found that there is a stable electric charge in our water basedsilicon complexes. It is well known in the literature that freeelectrons cannot exist for more than 1/10⁴ seconds in water. It ispostulated that the silicon acts as a clathrate to hold the atomichydrogen and the electrons separately and apart in a shell and allowsfor further chemical reactions under the right conditions. A process forstabilizing atomic hydrogen and solvated electrons in water would havewide implications in the world of chemistry and lead to many newchemical applications.

Clay is one of the most abundant minerals on earth. Clay has multipleuses because of its unique properties for hydrating in the presence offresh water. Clay is primarily an aluminum silicon complex with minorimpurities. Clays are used in zeolites as the first stage in therefinery process for cleaning and treating crude oils and catalysis.Clays are charged particles and in the presence of fresh water will“swell” and form a solid wall to allow water, oils and hazardousmaterials to be contained in clay pits. The swelling of clays presentsmajor problems in oil drilling operations by slowing down the rate ofpenetration by the drilling rigs into the earth. Clays are alsoresponsible for “tight sands”. Tight sands are heavily packed withvarious clays, with bentonite being one of the most common claysencountered in oil and gas reservoirs. The presence of clays in manyreservoirs prevents the use of water flood techniques for enhanced oilrecovery. As a result, many billions of barrels of crude oil areconsidered unrecoverable because of the swelling clays. As an example,the Department of Energy estimates that over 10 billion barrels of lightgravity crude are still in the Venango sandstones, a formation thatspreads across Pennsylvania, West Virginia, Ohio, and under Lake Erieinto Ontario, Canada. These formations are very shallow, ranging indepth from 200 to 1200 feet, but because of fresh water these formationshave only yielded 5% of the total oil in place. An inexpensive method ofbreaking up the clays present in these shallow formations could lead tothe ability to water flood these reservoirs, adding billions of barrelsof recoverable oil to the nation's supply and help achieve energyindependence.

Because the silicon compositions of the present invention arewater-soluble across a wide pH range, we decided to test whethermontmorillonite ((Na,Ca)(Al, Mg)₆(Si₄O₁₀)₃(OH)₆-nH₂O, hydrated sodiumcalcium aluminum magnesium silicate hydroxide) a clay commonly called“gumbo”, could be delaminated in fresh water using the siliconcompositions prepared in accordance with the present invention.Surprisingly, the gumbo fell apart into constituent particles in freshwater. Accordingly, the present invention thus provides a novel processfor delaminating clays, including montmorillonite clays. This discoveryshould lead to much improved enhanced oil recovery techniques and usesin tight gas sands, opening up permeability and porosity in thoseformations, particularly as montmorillonite is the major component ofbentonite, which is used in drilling muds. Likewise, improved breakingof bauxite—the clay-like material comprising aluminum ore—into itsconstituents may reduce the high costs of processing aluminum.

In other preferred embodiments, the present invention also includes amold and mildew treatment and prevention method. Mold and mildew createhuge problems, particularly in the humid areas of the United States andaround the world. Mold in housing is believed to be a leading cause ofasthma and other pulmonary disease. The silicon composition in the waterphase in accordance with the present invention was used to spray aconcrete stone 18″×18″×2″ that had an extensive growth of mildew. Themildew was destroyed in less than 30 minutes and the silicon formed asurface on the concrete that remained mildew free after 60 days.

Black mold had grown on several windows in an apartment and was causingallergic reactions. The silicate composition of the present inventionwas used to spray the aluminum panels where the mold was attaching. Themold was wiped off and the surface of the aluminum panels was rubbedwith the silicon composition. After 90 days there was no re-growth ofthe mold, indicating a very long-term application for prevention of moldin households.

In other preferred embodiments, the present invention includes aconcrete sealing method. A piece of concrete was immersed in the siliconcomposition and then was placed in a glass Mason jar containing 18 APIgravity crude oil. Oil is tenacious on concrete and cannot be readilyremoved even with steam cleaning. Surprisingly, when the treatedconcrete piece was extracted from the oil and dropped into a mason jarcontaining only fresh water, the oil immediately released from theconcrete and floated to the top of the water with no visible residue onor in the concrete piece. A coating that seals concrete and makes thesurface oleo-phobic would have commercial uses.

In other preferred embodiments, the tenacious, lubricating surfaceproduced on metals in accordance with the silicon/nitrogen compositionof the present invention indicated that an application would be to thecutting edges of knives, razor blades, saws, etc., for extending thelife of the edge. A stainless steel razor blade sold under theWalgreen's label was used as a test piece. A drop of the siliconsolution was wiped onto the blade surface. It was immediately apparentthat the blade had much more lubricity and that shave was much smootherand comfortable. These blades have a life of about 5 shaves before beingdiscarded. The treated blade shaved smoothly for 30 days and then wastreated again and the life of the edge was extended for another 30 days.Thus an inexpensive, easy to apply coating for razor blades, and allother sharp edges such as saws, knives and medical instruments has beendiscovered.

Similarly, two kitchen knives made of 410 stainless steel were used fora test. One knife was coated with the silicon/nitrogen complex and theother knife was untreated. A butane torch was then held against theuntreated knife and the metal became cherry red in one minute. Whencooled the surface had turned a bluish color indicating that the highheat had affected the properties of the stainless steel. The treatedknife was subjected to the same procedure and the metal did not turn toa cherry red for several minutes. The knife was allowed to cool downthere was no visible change in the color of the stainless steel.Stainless steel is considered to be an inert material and extremelydifficult to have a surface applied either electrolessly or byelectroplating. Accordingly, the present invention also includespreferred embodiments comprising new methods of enhancing the propertiesof stainless steel.

The ability to form a thin silicon nitrogen coating on medicalinstruments could lead to savings in the nation's ongoing attempts torein in medical costs. Bacterial contamination in the metal intersticesof medical instruments requires an extensive cleaning operation in anautoclave to destroy the bacterial contaminants. The silicon nitridecomposition forms a thin coating on metal surfaces and into the metalinterstices, filling up the holes and preventing bacteria from residingin the metal. This property should lead to a less costly method ofsterilization of operating room tools.

Other preferred embodiments of the present invention include ice releasetreatment compositions and methods. Two 3″×3″×⅛″ panels of 6061IT6aluminum were used. One was coated with a thin film of thesilicon/nitrogen composition in accordance with Example 2A (below) ofthe present invention, while the other panel was left untreated. Thesilicon/nitrogen coating was identified by EDAX (Energy Dispersive X-RayAnalysis). The two panels then had a thick water film formed on thesurfaces and were placed in a freezer at ˜18° C. (0° F.). After one hourthe panels were extracted from the freezer and the frozen surfacessubjected to a light bend test. The panel with the silicon/nitrogensurface immediately released the ice in a cracked almost monolithicsheet; the untreated panel would not release the ice sheet by cracking;the ice was melted off the surface of the aluminum substrate. Theaviation industry spends much time and money in deicing airplane wingswith a toxic chemical, ethylene glycol. A process that would prevent thewater from attaching to the aluminum and forming adhesive ice crystalswould be of commercial value and also to ease environmental problemscaused by the deicing chemicals.

Silicates have been widely used as flame-retardants since theirdiscovery in the 1860s. The property of silicates of swelling in thepresence of a flame and providing an insulating barrier is wellestablished. However, the use of silicates for flame retardation hasbeen limited in the conventional art, as they do not attach tenaciouslyto the surfaces of wood, cloth, or steel. It is thus another preferredembodiment of the present invention to provide flame-retardantcompositions and methods suitable for solving the related problems inthe conventional art. A sample of old, dried lumber was immersed in asilicate solution in accordance with the present invention and allowedto dry. It was then immersed in water, extracted, and allowed to dry. Abutane torch was used to hold a flame front on the surface of the driedlumber. The flame was held against the wood for five minutes and only aslight charring effect was noticeable. At no time did the timber supporta flame. We postulate that not only would the silicate compositionflameproof the wood, but also act as a surface to prevent formation ofmold and mildew and possible termite infestation. Two panels of 12 gauge1010 steel were used to test the efficacy of preferred embodiments ofthe invention including methods to impede heat transfer. One panel wasimmersed in the silicate composition for one minute and then extracted.The other panel was untreated. A butane torch was used to heat themetals to “cherry red”. The panels were held by hand and the flameapplied to the panels. The untreated panel reached cherry red conditionis less than a minute and transferred the heat down the length of thepanel and became too hot to hold. The treated panel took approximatelytwice as long to reach a cherry red condition but the heat transfer wassignificantly impeded. The silicate foamed up and impeded heat transferto the metal substrate. The panel could be held for several minutesbefore heat finally made the steel to hot too handle. The ability of thesilicon compositions to form a thin tenacious film on metals thatimpedes heat transfer into the basic metal has broad uses in severalcommercial areas. For example, steel pillars treated with siliconcompositions in accordance with the present invention could possiblyimpede enough heat transfer sufficiently to increase the period of timethey can withstand buckling and collapse.

Ethanol is an alcohol that is the product of fermentation of organicmatter. Ethanol is used as an additive to fuels to improve the cleanerburning of fuels to reduce emissions. In some countries such as Brazil,ethanol has been used solely as a renewable energy source. Ethanol isalso mandated in the U.S. as one of the additives for oxygenating fuels.The use of ethanol has wide political and environmental support. A majorbarrier to the further use of ethanol however, is that it is highlycorrosive to metals. A process that would reduce the corrosive activityof ethanol would find a very large market in the U.S. and around theworld. Accordingly, it is another preferred embodiment of the presentinvention to provide compositions and methods to reduce the corrosivityof ethanol to metal surfaces. This embodiment has been demonstrated byplacing 100 grams of ethanol in a glass beaker. Five grams of thesilicon composition in accordance with an embodiment of the presentinvention as described in Example 1A (below), was then added to theethanol. There was an immediate settling of salts from the solution andthe materials appeared to be incompatible. The ethanol was decanted fromthe salts into a separate beaker. A 1010 steel panel was immersed in theethanol solution for one minute and then extracted. A thin, tenaciousfilm had formed on the steel panel. The panel was left in the open airin the humid Houston, Tex. climate for thirty days. No corrosion wasvisible on that coated part of the panel. Surprisingly, the activeingredient in the silicon composition was apparently solubilized in thealcohol and maintained its electrochemical activity, which allowed fordeposition on a metal substrate using ethanol. Ethanol is sufficientlycorrosive that it is transported in stainless steel trucks andpipelines. The corrosive properties of ethanol preclude its wider use asan oxygenating agent for fuels. A product that could be added to ethanolto inhibit corrosion would thus be of substantial commercial value.

Accordingly, in some preferred embodiments, the present inventionprovides that ammonium hydroxide is added to a solution of sodiumsilicate, to which potassium hydroxide is added.

In other preferred embodiments, ammonium hydroxide is added to asolution of sodium silicate to which sodium hydroxide is then added.

In other preferred embodiments, the above processes may be varied bymaintaining the temperature of the resulting reaction mixture above 180°F. for a predetermined period of time. By way of illustration and notlimitation, said predetermined period of time may preferably be tenminutes or more, in some preferred embodiments.

In other preferred embodiments, ammonium hydroxide is added to asolution of sodium silicate, to which potassium hydroxide or sodiumhydroxide is added, and the resulting liquid is dehydrated in a lightmineral oil, and any resulting solids are removed by decantation.

In other preferred embodiments, ammonium hydroxide is added to asolution of potassium silicate, to which potassium hydroxide and/orsodium hydroxide is added, and the resulting liquid is dehydrated in alight mineral oil, and any resulting solids are removed by decantation.

In other preferred embodiments, ammonium hydroxide is added to asolution of sodium or potassium silicate, to which potassium hydroxideor sodium hydroxide is added, and the resulting liquid is dehydrated ina light mineral oil, and any resulting solids are removed bydecantation. The liquid phase is then added to the crankcase (as an oiladditive) or combustion chamber (as a 4-cycle fuel additive or as a2-cycle fuel or oil additive) of a 2-cycle or 4-cycle engine.

In other preferred embodiments, ammonium hydroxide is added to asolution of sodium or potassium silicate, to which potassium hydroxideand/or sodium hydroxide is added, to produce an aqueous solution of ionmixtures, and the resulting liquid is dehydrated in a light mineral oil,and any resulting solids are removed by decantation.

In other preferred embodiments, ammonium hydroxide is added to asolution of sodium or potassium silicate, to which potassium hydroxideor sodium hydroxide is added, to produce an aqueous solution of ionmixtures, and the resulting liquid is dehydrated in a light mineral oil,and any resulting solids are removed by decantation, and the resultingliquid is added to either the lubricating oil or fuel of an internalcombustion engine.

In other preferred embodiments, ammonium hydroxide is added to asolution of sodium or potassium silicate, to which potassium hydroxideor sodium hydroxide is added, to produce an aqueous solution of ionmixtures, and the resulting liquid is dehydrated in a light mineral oil,and any resulting solids are removed by decantation, and the resultingliquid is added to either the lubricating oil or fuel of a gasolineinternal combustion engine.

In other preferred embodiments, ammonium hydroxide is added to asolution of sodium or potassium silicate, to which potassium hydroxideor sodium hydroxide is added, to produce an aqueous solution of ionmixtures, and the resulting liquid is dehydrated in a light mineral oil,any resulting solids are removed by decantation, and the resultingliquid is added to either the lubricating oil or fuel of a dieselengine.

In other preferred embodiments, a thin adherent layer comprising siliconand nitrogen is electrolessly applied to metal wear surfaces byapplication of a precursor prepared by the combination of the aqueousion solution resulting from the mixture of sodium or potassium silicatewith ammonium hydroxide and an alkali metal hydroxide to produce anaqueous inorganic complex, with a light oil at a temperature sufficientfor dehydration, followed by incorporation of the complex into eitherlubricating oil or fuel.

In other preferred embodiments, an additive to lubricating oils thatsignificantly decreases the coefficient of friction is applied accordingto means described by the present invention.

Other preferred embodiments comprise a fuel additive for introduction ofa complex to accomplish the deposition of a silicon-nitrogen surface oninternal wear parts of an internal combustion engine. Other relatedpreferred embodiments comprise a lubricating oil additive forintroduction of a complex to accomplish the deposition of asilicon-nitrogen surface on internal wear parts of an internalcombustion engine.

Other preferred embodiments include an additive for ethanol withimproved corrosion resistance.

Other preferred embodiments include addition of the above compositionsand use of the above methods to provide compositions for applications tothe delamination of clays, particularly montmorillonite clays related tothe recovery of petroleum hydrocarbons.

Still other preferred embodiments include processes and materials forinhibiting corrosion, mildew, mold, heat, and fire, thus extending thelife of objects thus endangered, as well as providing for theirimprovement.

It is well understood in the chemical arts that ammonia, in the presenceof an alkali metal, can produce a volatile compound (i.e., sodiumazide). The ammonium is expelled from aqueous solutions by the presenceof alkali metal in the solution. Therefore, the ability to complexammonia in highly alkaline solutions with pH approaching 14 would createnovel chemicals complexes with a wide range of commercial uses.Surprisingly, it has now been found that when ammonium/alkaline metal isreacted with selected elements, the ammonium remained in solution at apH above 12. The complexes formed exhibit unusual electrochemicalproperties, such as forming new surfaces on metal substrates without theuse of applied external electromotive force.

Accordingly, it is an object of the present invention to provide uniqueand new alkaline chemical complexes of ions comprising, in someembodiments, a mixture of salts.

In some embodiments, a complex combination (Y)_(x)H(NH₄)₂HPO₄ includingammonium phosphate is provided, wherein Y can be any cation withpotassium being a preferred cation. In other embodiments, a complexcombination (Y)_(x)(H₈N₂)₄S including ammonium sulfate is provided,wherein Y can be any cation with sodium being a preferred cation. Inother embodiments, a complex combination (Y)_(x)C₂H₇NO₂ includingammonium acetate is provided, wherein Y can be any cation. In otherembodiments, a complex combination (Y)_(x)CH₅NO₃ including ammoniumbicarbonate is provided, wherein Y can be any cation. In otherembodiments, a complex combination (Y)_(x)B₄H₈N₂O₇ including ammoniumborate is provided, wherein Y can be any cation. In other embodiments, acomplex combination (Y)_(x)H₂SO₄(BiNH₄)_(x) is provided. In otherembodiments, a complex combination (Y)_(x)(NH₄)Si_(x) is provided.

BRIEF DESCRIPTION OF THE DRAWING FIGURES

FIG. 1 is a ²⁹Si NMR spectrum of an aqueous solution comprising acomplex mixture of ions in accordance with the present invention.

FIG. 2 is a ²⁹Si NMR spectrum of an aqueous solution comprising acomplex mixture of ions in accordance with the present invention.

FIG. 3 is a summary scan XPS spectrum of a steel panel treated with anaqueous solution comprising a complex mixture of ions in accordance withthe present invention.

FIG. 4 is a high-resolution XPS spectrum of the Si2p peak of a steelpanel treated with an aqueous solution comprising a complex mixture ofions in accordance with the present invention.

FIG. 5 is a high-resolution XPS spectrum of the N1s peak of a steelpanel treated with an aqueous solution comprising a complex mixture ofions in accordance with the present invention.

FIG. 6 is an EDAX spectrum of a steel panel treated with an aqueoussolution comprising a complex mixture of ions including in accordancewith the present invention.

FIG. 7 is an EDAX spectrum of an aluminum panel treated with an aqueoussolution comprising a complex mixture of ions in accordance with thepresent invention.

FIG. 8 is a summary scan XPS spectrum of a steel panel treated with anaqueous solution comprising a complex mixture of ions in accordance withthe present invention.

FIG. 9 is a high-resolution XPS spectrum of the Si2p peak of a steelpanel treated with an aqueous solution comprising a complex mixture ofions in accordance with the present invention.

FIG. 10 is a high-resolution XPS spectrum of the N1s peak of a steelpanel treated with an aqueous solution comprising a complex mixture ofions in accordance with the present invention.

FIG. 11 is an EDAX spectrum of a steel panel treated with an aqueoussolution comprising a complex mixture of ions including silicon andtungsten in accordance with the present invention.

FIG. 12 is an EDAX spectrum treated with an oil-based solutioncomprising silicon in accordance with the present invention.

FIG. 13 is an EDAX spectrum of a steel panel treated with an aqueoussolution of complex ions including silicon and molybdenum in accordancewith the present invention.

FIG. 14 is an EDAX spectrum of a steel panel treated with a solutionmade with ferrosilicon in accordance with the present invention.

FIG. 15 is an EDAX spectrum treated with an oil-based solutioncomprising silicon in accordance with the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Herein will be described in detail specific preferred embodiments of thepresent invention, with the understanding that the present disclosure isto be considered an exemplification of the principles of the invention,and is not intended to limit the invention to that illustrated anddescribed herein. The present invention is susceptible to preferredembodiments of different forms or order and should not be interpreted tobe limited to the specifically expressed methods or compositionscontained herein. In particular, various preferred embodiments of thepresent invention provide a number of different configurations andapplications of the inventive method, compositions, and theirapplications.

EXAMPLES Composition 1 Example 1A

The following equipment was used in experiments described below: 4000 mlKimax beaker; Thermolyne Cimarec 2 with magnetic mixer; Acculab V600scale with a 0.1 gram readability; and Accurite 100°-400° F.thermometer.

A solution comprising a complex mixture of ions was produced by thesteps of adding the following reagents to the beaker: 200 ml water; 50grams of sodium silicate (solid); 25 grams of ammonium hydroxide (29°Baume); 50 grams of potassium hydroxide (flakes).

A slight ammonia odor was detectable. The solution was forced intoexotherm by heating while stirring. The temperature was maintained above180° F. for 10 minutes and then turned off. The solution continued itsexotherm for several more minutes and then was allowed to cool down. Thesolution was examined by liquid-phase ²⁹Si NMR (Nuclear MagneticResonance) Spectroscopy, which identified SiO₄ as illustrated by thespectrum of FIG. 1.

Example 1B

A solution comprising a complex mixture of ions was produced inaccordance with Example 1A except that sodium hydroxide was substitutedfor potassium hydroxide. The solution was examined by liquid-phase ²⁹SiNMR (Nuclear Magnetic Resonance) Spectroscopy, which identified SiO₄ asillustrated by the spectrum of FIG. 2.

Example 2A

A 1010 steel coupon was immersed in the solution comprising a complexmixture of ions prepared in accordance with Example 1A when thetemperature was below 140° F. with no external electromotive forcerequired. A visible, tenacious film formed on the steel panel. The panelwas examined by XPS (X-Ray Photoelectron Spectroscopy) and the presenceof silicon and nitrogen on the surface of the panel was detected, asillustrated by FIG. 3 (summary scan spectrum), FIG. 4 (high-resolutionspectrum of Si2p peak), and FIG. 5 (high-resolution spectrum of N1speak). Another steel panel immersed in this solution was analyzed viaEDAX with the results illustrated in the spectrum of FIG. 6 ¹. Analuminum panel immersed in this solution was analyzed via EDAX with theresults illustrated in the spectrum of FIG. 7.¹ Table 4 provides semi-quantitative, ZAF-corrected and normalized EDAXresults (atomic-%).

Example 2B

A 1010 steel coupon was immersed in the solution comprising a complexmixture of ions prepared in accordance with Example 1B when thetemperature was below 140° F. with no external electromotive forcerequired. A visible, tenacious film formed on the steel panel. The panelwas examined by XPS and the presence of silicon and nitrogen on thesurface of the panel was detected, as illustrated by FIG. 8 (summaryscan spectrum), FIG. 9 (high-resolution spectrum of Si2p peak), and FIG.10 (high-resolution spectrum of N1s peak).

Example 3

In each of two glass beakers, 70 grams of montmorillonite I clay wasimmersed in 100 grams of fresh water. In one beaker 5 ml of the solutioncomprising a complex mixture of ions prepared in accordance with Example1A was added to the fresh water. Both beakers were observed closely. Inthe beaker to which the inventive solution had been added, the clayslowly began to delaminate and fall to the bottom of the beaker asfinely divided particles. In the other beaker there was no visibledelamination of the clay. After 24 hours the clay in treated beaker hadbeen completely separated into constituent elements. In the otherbeaker, the clay was still intact and there was a slight indication ofthe clay swelling.

Example 4 Preparation of “Con1”

600 grams of Penreco® Drakeol® 5 was added to a glass beaker with 120grams of the solution comprising a complex mixture of ions prepared inaccordance with Example 1A. The heater was turned on with continuousstirring. The temperature of the mixture was raised above 265° F. andboiled at that temperature for 20 minutes, at which time salts formedand precipitated from the solution to the bottom of the beaker. The oilphase was bright and clear. This solution will hereinafter be referredto as “Con1”.

Example 5 Preparation of “Additive 1”

5 grams of Con1, prepared in accordance with the procedure described inExample 4, was mixed with 100 grams of Drakeol® 5 and stirred. Theresulting solution will hereinafter be referred to as “Additive 1”. 10ml of the Additive 1 was mixed into 200 ml of diesel fuel. The Additive1 was completely miscible in the diesel fuel.

Example 6

4 grams of Additive 1 and 225 grams of unleaded gasoline were mixed in abeaker. The Additive 1 was miscible in the gasoline.

Two-Cycle Engine Tests

The mixture prepared in accordance with Example 6 was used inexperiments for testing on two-cycle engines to measure fuel economy and“do no harm”. The engine chosen for the test procedure was a Homelitetwo-cycle leaf blower with a 30 cc engine. The need to turn the blowerat high rpm places a load on the small engine. The engine is run in the7200 rpm range with a constant load at all times. Two-cycle engines,which typically use a mixture of fuel to oil at a 50:1 ratio, aredifficult to lubricate and are not fuel-efficient. The two-cyclelubricants currently being widely used to lubricate and protect againstengine damage contain a large amount of “bright stock”, a heavy fractionin oils that is very toxic and polluting. A two-cycle engine of thistype, if not properly lubricated, will typically seize up within 20minutes or less. It would thus not be expected that a lubricant madewith a silicon-containing component would provide protection for atwo-cycle engine against seizure and failure.

Example 7

The fuel was prepared using standard two-cycle oil at a fuel:oil mixratio of 50:1. Two control runs were made with a new engine; each runusing 225 grams of gasoline mixed with 4.5 grams of standard two-cycleoil. A “baseline” control run length (i.e., time to fuel exhaustion) wasdetermined by averaging the lengths of the two runs, which resulted in abaseline of 29 minutes, 45 seconds. A one-pint volume of treatedtwo-cycle oil was then prepared that contained 5% (by weight) of Conl,which had been prepared in accordance with Example 4. Four identicaltest runs were then performed; each using 225 grams of gasoline mixedwith 4.5 grams of the treated two-cycle oil, running the test engineuntil it shut down for lack of fuel. The time to fuel exhaustion wasmeasured in each of the four tests. Results from the four runs were asshown below in Table 1: TABLE 1 Run Time (min, sec) Baseline 29 minutes,45 seconds 1 34 minutes, 40 seconds 2 36 minutes, 18 seconds 3 32minutes, 0 seconds 4 32 minutes, 15 seconds

The average of the four test runs (using the Con1 as an additive) was 33minutes and 13 seconds compared with control runs (baseline—no additive)of 29 minutes and 45 seconds or a decrease in fuel usage for identicalruns. There was also a noticeable reduction in particulate emissionswith the test mixtures prepared using the Con1 additive. The engine didnot seize and, in fact, appeared to run smoother with the test mixturesprepared using Con1. This test demonstrated that the Con1 additiveimproved fuel economy and reduced emissions, and did not harm theengine.

Example 8

300 grams of methyl ester (Soy Methyl Ester, Columbus Foods, Chicago,Ill.) were placed in a beaker to which 15 grams of the solutioncomprising a complex mixture of ions prepared in accordance with Example1A was added. The solution was heated to above 200° F., began to foam,and on cooling formed soap. This example mixture was deemed not to be acandidate as a fuel or lubricant additive.

Example 9

5 grams of Con1 was added to 100 grams of methyl ester, in which it wascompletely miscible. The resulting mixture was used as a fuel additiveat a rate of approximately one ounce of fuel additive mixture to 10gallons of automotive gasoline or diesel fuel.

Example 10

0.1 grams ammonia paratungstate (solid) was added to 40 grams of thecomplex mixture of ions produced in accordance with Example 1A withstirring until the solid dissolved. A 1010 steel panel was then immersedin the resulting solution and extracted after 1 minute. A visible thin,tenacious, adherent film had formed on the metal substrate. The panelsurface was examined by EDAX and the results that were obtained areillustrated by the spectrum shown in FIG. 11. The presence of tungstenand silicon was detected on the surface of the metal.

The above-described solution of ammonia paratungstate was thendehydrated with Drakeol® 5 using the general procedure described inExample 4, by heating to above 300° F. with stirring until salts formedand precipitated to the bottom of the glass beaker. A 1010 steel panelwas inserted in the resulting solution while the temperature was about180° F. and a visible, thin film was present on the panel. This panelwas then analyzed by EDAX. The results that were obtained areillustrated by the spectrum provided at FIG. 12. The presence oftungsten and silicon was detected on the surface.

Example 11

0.1 grams of ammonia molybdate (solid) was added to 40 grams of thecomplex mixture of ions produced in accordance with Example 1A, withstirring until the solid dissolved. A 1010 steel panel was then immersedin the resulting solution and extracted after 1 minute. A visible, thin,tenacious, adherent surface had formed on the metal. The panel surfacewas then analyzed by EDAX. The results are illustrated by the spectrumprovided at FIG. 13. Silicon and molybdenum were detected on the metalsurface.

The electroless deposition of tungsten and molybdenum from aqueoussolutions is another novel characteristic of the present invention. Theconventional art teaches that such deposition is not possible. Forexample, the conventional text by Frederick A. Lowenheim,“Electroplating: Fundamentals of Surface Finishing” (1977) McGraw-HillBook Company (TX), ASIN 0070388369 (pg. 141) teaches that “from thestandpoint of their electrode potentials, it should be possible toelectroplate such metals as tungsten and molybdenum from aqueoussolutions with a pH of about 5. Nevertheless (in spite of claims in theliterature) these metals cannot be deposited in pure form from aqueoussolutions”. Therefore, the electroless deposition of tungsten andmolybdenum, together with other refractory metals, from aqueoussolutions is new in the art. Silicon/refractory metal surfaces wouldfind wide fields of commercial use in, for example, protection of metalsurfaces, reducing coefficients of friction, inhibiting corrosion,hardening metals and, as previously described, could impart high heatresistance. Other specific areas of potential usage include as fueladditives for jet turbine engines in aircraft in addition to ground useturbine applications. A thermal barrier could easily be formed by themethods of the present invention for use on components designed forhostile thermal environments, such as super-alloy turbines and thecombustor and augmentor components of gas turbine engines. Thesilicon-nitrogen could diffuse into the surface of the jet turbinecomponents and form a heat resistant (and potentially reflective)coating. There is no method known today for coating jet turbine enginecomponents that does not involve taking the engine apart and eitherreplacing components or applying metallizing sprays. The methodscurrently used obviously place a heavy financial burden on turbineowners because of both the downtime and the replacement costs for partsand materials.

Another commercial use segment of significant potential value is burnersfor industrial combustion systems, such as gas-fired furnaces forheat-treating and low-NO_(x) industrial pyrolysis furnaces. Thecombustion of natural gas generates substantial quantities of nitrogenoxides and much time and money has been spent on improving natural gasburner designs to lower their NO_(x) emissions. The new low NO_(x)burners will reduce NO_(x) emissions for periods of time, but it isexpected that metals in natural gas in the parts per billion range willslowly build up on the nozzles of the burners and affect flow patternsto increase NO_(x) emissions. A heat resistant coating on industrialburners would significantly extend the useful life of the burners withcontinued low NO_(x) emissions. Such a heat resistant coating has thefurther advantage of potentially permitting the use of less expensiveburner materials. The thin coating of the silicon nitride, for example,could improve the flow characteristics of combustion gases givingfurther benefits in terms of burner design options for lowering NO_(x)emissions and improving burner performance.

Four—Cycle Engine Tests

Example 12

For the tests of this Example, a 2000 model year Lincoln Town Car with a4.6-liter engine and an automatic transmission was used. A base linefuel consumption figure was first established by running the vehicle forover 300 miles at about 72 MPH continuously with regular unleaded fuel.The resulting baseline average fuel consumption was 22.4 MPG. The fueltank was then refilled using the additive in accordance with the presentinvention as described above in Example 9 (one ounce of fuel additiveper 10 gallons of Diamond Shamrock brand regular unleaded fuel). Thetest car was then driven over approximately the same highway at aboutthe same speed (72 MPH) and at generally the same ambient conditions.The onboard computer indicated that the car achieved 25.9 MPG with theadditive-treated fuel. This amounts to a decrease in fuel usage of 3.5gallons per tank, or a 15.6% improvement in fuel economy.

Example 13

A 1991 Ford F150 pickup with a 4.9 L engine, a standard five speedmanual transmission, and 325,000 miles of usage, which had anestablished baseline of 15.5 MPG using regular unleaded fuel, was testedusing Additive 1 prepared in accordance with the procedure describedabove in Example 5, using 1 ounce of Additive 1 per 10 gallons regularunleaded fuel. Under test conditions similar to those described abovewith respect to Example 12, this test vehicle obtained a fuel usage of19.67 MPG, which is a fuel economy benefit of 26.9%.

Example 14

A 1998 Chevrolet CK3500 4×4 with a 6.5-L diesel engine with 184,165miles was used as a test vehicle. A baseline mileage was established at14.7 MPG. One test run was then made with the test vehicle to establisha baseline. Three test runs were then made using Additive 1 in standardon road automotive diesel fuel. The ratio of addition was 1 ounce ofAdditive 1 to 10 gallons of diesel fuel. The results were as follows inTable 2: TABLE 2 Tank Fuel Consumption (MPG) Change (%) 1 15.9 +8.2% 216.8 +14.7 3 17.0 +15.6

Example 15

For the following Example, a diesel-electric generator with a 150 KWFiat engine was used. The Fiat engine had 13,850 hours of use prior totesting. The purpose of the test was to determine the effect if any ofadditives prepared in accordance with the present invention on fuelefficiency and environmental emissions. The engine typically releasedsubstantial particulates upon start-up, and generally continued visiblesmoking during operation. The generator was set at 33% load capacity forthis test. A base line of fuel usage was determined by filling the fueltank to the top of the tank. The diesel engine was then started, and thegenerator was run with a 33% load for 8 hours. The fuel tank was thenrefilled and the amount used to fill the tank was noted to determinefuel consumption. The fuel tank capacity was 100 gallons. TABLE 3 RunFuel (gal) Time (hrs) Fuel Consumption (gal/hr) Base 32.6 8 4.075 Test83.6 23 3.634

As noted in Table 3, the base line fuel consumption (with no Additive 1)was 4.075 gallons per hour, as compared to the test fuel consumption of3.634 gallons per hour using Additive 1 as described above. This amountsto a reduction in fuel consumption of approximately 9.24%.

Further, as noted, the test engine had relatively heavy particulateemissions during startup for the baseline run, which is not atypical fora diesel engine. The engine had noticeably significant reductions instartup particulates after treatment, indicative of improvement in thecombustion process. TABLE 4 Elemental Analysis via EDAX (ZAF-Corrected,Normalized) Atomic-% (ZAF Corrected, Normalized) Example Ex. 2A Ex. 2AEx. 10 Ex. 10 (steel) (alum.) (aq.) (oil) Ex. 11 Ex. 17 Ex. 18 SpectrumElement Oxygen −12.642 16.764 −1.911 −4.334 −6.289 −8.272 −2.186 Sodium— 0.378 — — — — — Aluminum — 80.970 — — — — — Silicon 0.389 1.475 1.5160.346 0.518 0.315 0.499 Phosphorus 0.005 0.098 0.003 −0.015 −0.009 0.098−0.015 Chlorine 0.126 0.063 −0.015 −0.009 0.104 0.092 0.091 Calcium —0.161 — — — — — Iron 111.777 0.091 99.904 103.760 105.279 107.776101.172 Molybdenum −0.016 — −0.002 0.003 0.051 −0.008 −0.004 Manganese0.360 — 0.474 0.239 0.345 — 0.464 Tungsten — — 0.032 0.010 — — −0.021Total 100.000 100.000 100.000 100.000 100.000 100.000 100.000

Composition 2

In Merkl, a study of low purity silicon/potassium is described (seeExample 1 of Merkl at column 23). As discussed above, the Merki methodemployed an endothermic phase that lasted 6 hours followed by anexothermic phase that lasted for 45 minutes. In accordance with certainembodiments of the present invention, a reaction scheme was employedcomprising a novel variant wherein the rate of addition of the alkalimetal is varied and no endothermic reaction is employed.

Example 16

This Example used 616 grams of ferrosilicon rocks containing about 75%silicon with about 25% iron, and a rock size of approximately 1 cm(about ½ inch). Other reagents included 2000 grams ammonium hydroxide(26° Baume) and 616 grams potassium hydroxide (flakes). The ingredientswere added as quickly as possible and then forced into an exothermicreaction by applying heat to the vessel. The exothermic reaction lastedfor 45 minutes and a clear viscous fluid resulted. Specific gravity wasthen measured at 1.2. The resulting solution was decanted from theunreacted ferrosilicon rocks.

Example 1 7

Approximately one hour after preparation of the solution as described inExample 16, a panel of 1010 steel was immersed in the solution for 30seconds and then extracted. The panel was then analyzed via EDAX. Theanalytical results are provided in the spectrum provided at FIG. 14.Silicon was detected on the surface of the metal.

Example 18 Preparation of “Con2”

600 grams of Drakeol® 5 was placed in a 4000-ml beaker and 120 grams ofa ferrosilicon solution prepared in accordance with Example 16 wasadded. The solution was heated with stirring. Above 300° F. saltsprecipitated, leaving a clear and bright solution, indicating that allthe water had been removed. The heat was turned off and the temperaturedropped to 180° F., at which time a panel of 1010 steel was immersed inthe oil solution for 1 minute. The panel was extracted and a thin,tenacious film was observed on the metal. The panel was then analyzedvia EDAX. The result is provided in the spectrum shown in FIG. 15.Silicon was detected on the metal surface, which indicates that asoluble silicon species in the oil is deposited on the metal from theoil-based solution. This solution is hereinafter referred to as “Con2”.

Con2 was added to 150 solvent neutral BP 901 base oil at a ratio of 1gram Con2 to 20 grams solvent neutral oil, to provide make an oil andlubricant additive. Although 150 solvent neutral BP 901 base oil wasused in this Example, those skilled in the art will recognize that anysimilar oil, such as any base oil manufactured from solvent refinedparaffinic lube distillates or a US 350H group 2 oil may be used withsatisfactory results.

Four—Cycle Engine Tests

Example 19

5 grams of Con2 prepared in accordance with Example 18 was stirred into100 grams of Drakeol® 5. The resulting mixture, referred to hereinafteras “Additive 2” was placed in the fuel tank of the model year 2000Lincoln Town Car previously referred to in the context of Example 12, atthe rate of one ounce of the Additive 2 per ten gallons of regularDiamond Shamrock brand unleaded fuel. As noted with respect to Example12, base line fuel consumption for this vehicle had previously beenestablished at 22.4 MPG. The test vehicle was then driven 310 miles atan average speed of 72 MPH. During the first 100 miles the onboardcomputer registered at 24.5 MPG. For the balance of the test the onboardcomputer registered 27.4 MPG, for an improvement in fuel economy of 5MPG or 22.3%. This represents a further increase in fuel efficiency overthe Example 12 results using Con1 of 3.5 mpg or 15.6%.

Example 20

In this Example, Additive 2 was tested in the Ford 150 pickup of Example13 (now with 334,000 miles of usage) at the ratio of 1 ounce per 10gallons of Diamond Shamrock brand regular unleaded fuel. The vehicle wasthen driven for 220 miles and an average of 19.37 MPG was achieved,which is similar to the result achieved in Example 13.

Additional Metal Tests

Example 21

In this Example, a stoichiometric amount of ammonium phosphate monobasicis dissolved in water. The pH of the solution is raised to 14 by theaddition of an alkali metal hydroxide. The resulting solution is thenheated to above 180° F. and maintained at elevated temperature for 20minutes or until the odor of the ammonia is no longer present. A panelof 1010 steel is then immersed in the solution for 20 seconds and athin, tenacious film is formed on the metal. A stainless steel kitchenknife is immersed in the solution for 30 seconds, removed, and dried. Athin tenacious film formed on the stainless steel. Stainless steel is apassive metal alloy and does not accept a new surface withoutsignificant preparation in a dilute nitric acid solution followedimmediately by placement in a plating bath with applied electromotiveforce in order to obtain a new surface. The solution containsammonium/alkali metal/phosphorous and water. The solution is thendehydrated thermally in a hydrocarbon oil. A panel of 1010 steel wasimmersed in the oil solution for 30 seconds and a thin tenacious filmformed on the steel panel.

Example 22

In this Example, a stoichiometric amount of ammonium sulfate isdissolved in water. The pH of the aqueous solution is raised to above 12and the solution is then heated to above 180° F. and held at thattemperature until the odor of ammonia is no longer present. A stainlesssteel knife is then immersed in the solution and a thin, tenacious filmis formed on the stainless steel piece. The solution containsammonium/alkali metal/sulfur and water. The solution is then thermallydehydrated in a hydrocarbon oil. A panel of 1010 steel was immersed inthe oil solution for 30 seconds and a thin tenacious film formed on thesteel panel.

Example 23

In this Example, ammonium acetate is dissolved in water. The pH of thesolution is then raised to above 12 and held at a temperature above 180°F. until the odor of ammonia is no longer present. The solution containsammonium/alkali metal/carbon and water. The solution was then thermallydehydrated in a hydrocarbon oil.

Example 24

In this Example, a stoichiometric amount of ammonium borate is dissolvedin water. The pH of the solution is then raised to above 12 by theaddition of an alkali metal and then heated for 20 minutes or until theodor of ammonia is no longer present. The solution containsammonium/alkali metal/boron. A stainless steel panel is immersed in thesolution and a thin, tenacious film formed on the stainless steel. Thesolution is then dehydrated thermally in a hydrocarbon oil. A panel of1010 steel was immersed in the oil solution and a thin tenacious filmformed on the metal.

Example 25

In this Example, 54.4 grams of bismuth BB's (small spheres) is mixedwith boiling H₂SO₄ and water. The solution is decanted and the bismuthBB's are washed with water, dried, and then weighed. A total of 2.4grams of bismuth was dissolved into the solution, which had a pH below2. The solution was raised to a pH of 8 by adding ammonium hydroxide,and the pH was further raised above 12 by the addition of potassiumhydroxide. The solution was then heated to above 180° F. until the odorof ammonia was no longer present. A panel of 1010 steel was immersed inthe solution and a thin, tenacious film formed on the steel panel. Thesolution was then thermally dehydrated in a hydrocarbon oil. A panel of1010 steel was immersed in the oil solution for 30 seconds and a thintenacious film formed on the steel panel.

Example 26

In this Example, ferrosilicon (75% Si) is placed in a reaction vessel.Ammonium hydroxide, an alkali metal hydroxide, and water are then placedin the reaction vessel. The vessel is then heated to 180° F. and anexothermic reaction occurs which continues until the solution is tooviscous to support further reaction.

A solution of ethanol/methanol is placed in a glass beaker. A measuredamount of the aqueous silicon solution is poured into the alcoholmixture. There is an immediate precipitation of salts. A panel of 1010steel is then immersed in the solution for 30 seconds, and a thintenacious film formed on the steel panel.

The aqueous silicon solution is then thermally dehydrated into ahydrocarbon oil and some of the silicon becomes partly soluble in theoil. The sulfur oil of Example 22 (above) is then mixed with the siliconoil and the oils are miscible. A beaker of ethanol/methanol is added toa vessel and the sulfur/silicon oil is added to the ethanol/methanolsolution. A 1010 steel panel is then immersed in the sulfur/silicon oilsolution for 30 seconds and then extracted. A thin tenacious film hadformed on the steel panel. Ethanol is currently being touted as a methodof reducing dependency on oil resources. Ethanol has limitations in thetransport and handling of the solution. Ethanol is extremely corrosive;thus, any system that would allow for film forming on metals thatcontact ethanol would be valuable.

Example 27

Bio-diesel is also being touted as a method to reduce reliance on oil.Bio-diesel, for example, is a mixture of 80% hydrocarbon diesel fuel and20% methyl esters. The methyl ester is derived from vegetable oils,primarily soybean oils, and is processed to remove the glycerin. Themethyl ester can then be added to hydrocarbon diesel at any ratio andused for combustion purposes. The aqueous solution of Example 1A aboveis first thermally dehydrated in a hydrocarbon oil. The resultingsolution is then added to the methyl esters and becomes completelymiscible. A 1010 steel panel is immersed in the modified methyl esterfor 30 seconds. A thin tenacious film is deposited on the steelsubstrate. Methyl esters can thus be used to bring thin tenacious filmsonto all the metal parts in internal combustion engines.

While the preferred embodiments of the invention have been shown anddescribed, modifications thereof can be made by one skilled in the artwithout departing from the spirit and teachings of the invention. Theembodiments described herein are exemplary only, and are not intended tobe limiting. Many variations and modifications of the inventiondisclosed herein are possible and are within the scope of the invention.Accordingly, the scope of protection is not limited by the descriptionset out above, but is only limited by the claims which follow, thatscope including all equivalents of the subject matter of the claims.

The examples provided in the disclosure are presented for illustrationand explanation purposes only and are not intended to limit the claimsor embodiment of this invention. While the preferred embodiments of theinvention have been shown and described, modification thereof can bemade by one skilled in the art without departing from the spirit andteachings of the invention. Process criteria, pendant processingequipment, and the like for any given implementation of the inventionwill be readily ascertainable to one of skill in the art based upon thedisclosure herein. The embodiments described herein are exemplary only,and are not intended to be limiting. Many variations and modificationsof the invention disclosed herein are possible and are within the scopeof the invention. Use of the term “optionally” with respect to anyelement of the invention is intended to mean that the subject element isrequired, or alternatively, is not required. Both alternatives areintended to be within the scope of the invention.

The discussion of a reference in the Description of the Related Art isnot an admission that it is prior art to the present invention,especially any reference that may have a publication date after thepriority date of this application. The disclosures of all patents,patent applications, and publications cited herein are herebyincorporated herein by reference in their entirety, to the extent thatthey provide exemplary, procedural, or other details supplementary tothose set forth herein.

1. An additive for improving engine performance comprising, in aqueoussolution, ammonium, an alkali metal, and a coating component selectedfrom the group consisting of phosphorus, sulfur, carbon, bismuth, boron,silicon, and combinations thereof.
 2. The additive of claim 1 furthercomprising a hydrocarbon oil.
 3. An engine additive consistingessentially of a source of ammonium ions, a source of alkali metal ions,a coating component, and a hydrocarbon.
 4. The additive of claim 3wherein the coating component is selected from the group consisting ofphosphorus, sulfur, carbon, bismuth, boron, silicon, and combinationsthereof.
 5. The additive of claim 3 wherein the coating component isselected from the group consisting of ammonium phosphate, ammoniumsulfate, ammonium acetate, ammonium borate, metallic bismuth dissolvedin sulfuric acid solution, ferrosilicon, and combinations thereof. 6.The additive of claim 3 wherein the hydrocarbon comprises an oilselected from the group consisting of solvent neutral oils, syntheticoils, mineral oils, vegetable oils, methyl esters, and combinationsthereof.
 7. A method for preparing an additive for improving fuelperformance comprising the steps of preparing an aqueous mixturecomprising ammonium, an alkali metal, and a coating component selectedfrom the group consisting of phosphorus, sulfur, carbon, bismuth, boron,silicon, and combinations thereof, and heating the aqueous mixture. 8.The method of claim 7 further comprising dehydrating the aqueousmixture.
 9. The method of claim 8 further comprising precipitatingsalts.
 10. The method of claim 9 further comprising solubilizing in ahydrocarbon oil.
 11. An aqueous composition with a pH greater than 9 andcapable of solubilization in hydrocarbons for improving fuel economy,said solution being formed by combination of an alkali metal, a sourceof ammonium ions, and a coating component selected from the groupconsisting of phosphorus, sulfur, carbon, bismuth, boron, silicon, andcombinations thereof.
 12. The aqueous composition according to claim 11wherein the alkali metal is sodium.
 13. The aqueous compositionaccording to claim 11 wherein the alkali metal is potassium.
 14. Theaqueous composition according to claim 11 wherein the source of ammoniumions is selected from the group consisting of ammonium phosphate,ammonium sulfate, ammonium acetate, ammonium borate, ammonium hydroxide,and combinations thereof.
 15. The aqueous composition according to claim11 wherein said aqueous composition is solubilized in a hydrocarbon oilselected from the group consisting of solvent neutral oils, syntheticoils, mineral oils, vegetable oils, methyl esters, and combinationsthereof, such that the solubilized composition is miscible and stable indiesel fuel.
 16. A method of preparing an aqueous composition comprisingproviding a source of ammonium ions, providing a source of alkali metalions, providing a coating component, solubilizing said mixture in ahydrocarbon liquid to produce an additive, and applying said additive toan internal wear surface of an internal combustion engine.
 17. Themethod of claim 16 wherein the coating component is selected from thegroup consisting of phosphorus, sulfur, carbon, bismuth, boron, silicon,and combinations thereof.
 18. The method of claim 17 wherein thehydrocarbon liquid is selected from the group consisting of solventneutral oils, synthetic oils, mineral oils, vegetable oils, methylesters, and combinations thereof.
 19. The method of claim 18 wherein thesource of ammonium ions is selected from the group consisting ofammonium phosphate, ammonium sulfate, ammonium acetate, ammonium borate,ammonium hydroxide, and combinations thereof.
 20. The method of claim 19further comprising dehydrating the aqueous mixture and precipitatingsalts.
 21. The method of claim 19 wherein at least one additional metalfrom Groups I-VIII of the Periodic Table is also solubilized in theadditive.
 22. The method of claim 19 further comprising electrolesslydepositing a silicon surface on at least one conductive substrate. 23.The method of claim 16 wherein the internal combustion engine comprisesa diesel engine.
 24. The method of claim 16 wherein the internalcombustion engine comprises a gasoline engine.
 25. The method of claim16 wherein the fuel consumption of the engine is improved by at least5%.